Polymeric dyes derived from bis-reactive methylene compounds and aromatic di-aldehydes for paper

ABSTRACT

Polymeric dyes of the general formula I ##STR1## where A is the radical of a methylene-active compound, which may or may not be quaternized, 
     B 1  and B 2  are bridge members which may or may not be quaternized or B 2  may be a direct bond, 
     n is number &gt;1, 
     p is the number of positive charges, 
     R is hydrogen, chlorine, bromine, hydroxyl, C 1  -C 8  -alkyl, nitro, C 1  -C 8  -alkoxy, C 1  -C 8  -alkoxycarbonyl, cyano, hydroxycarbonyl, unsubstituted or substituted carbamyl or unsubstituted or substituted amino, 
     R 1  is hydrogen, chlorine, hydroxyl, C 1  -C 4  -alkyl or C 1  -C 4  -alkoxy or 
     R and R 1  together are an unsubstituted or substituted fused ring, or R and R 1  together with B 2  are a heterocyclic radical and 
     A.sup.⊖ is an anion.

This is a continuation of application Ser. No. 217,747, filed Dec. 18,1980, which is a continuation of Ser. No. 125,905 filed Feb. 29, 1980,both abandoned.

The present invention relates to dyes of the general formula I ##STR2##where A is the radical of a methylene-active compound, which may or maynot be quaternized,

B¹ and B² are bridge members which may or may not be quaternized or B²may be a direct bond,

n is a number >1,

p is the number of positive charges,

R is hydrogen, chlorine, bromine, hydroxyl, C₁ -C₈ -alkyl, nitro, C₁ -C₈-alkoxy, C₁ -C₈ -alkoxycarbonyl, cyano, hydroxycarbonyl, unsubstitutedor substituted carbamyl or unsubstituted or substituted amino,

R¹ is hydrogen, chlorine, hydroxyl, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy or

R and R¹ together are an unsubstituted or substituted fused ring, or Rand R¹ together with B² are a heterocyclic radical and

A.sup.⊖ is an anion.

Radicals B¹ may be symmetrical or unsymmetrical. They may be aliphaticor aromatic and may contain heteroatoms; examples are unsubstituted orsubstituted alkylene radicals which may or may not be interrupted byoxygen, --NH--, sulfur, carbamyl, carbonyloxy, ##STR3## unsubstituted orsubstituted phenylene, diphenylene or naphthylene radicals, or saturatedcycloalkylene radicals which may or may not contain hetero-atoms. Morespecific examples of B¹ are: ##STR4##

B² may be a direct bond or, if it is a bridge member, it is asymmetrical or unsymmetrical radical derived from an amine, oligoamineor polyamine; examples are: ##STR5## where T is a straight-chain orbranched alkylene radical which is unsubstituted or substituted byhydroxyl, C₁ -C₄ -alkoxy, chlorine or bromine, or is a phenyleneradical, and

R² is hydrogen or unsubstituted or substituted alkyl, and

B¹ and r have the stated meanings.

The radicals A are derived from methylene-active compounds; specificexamples are: ##STR6## where X is hydrogen, cyano, C₁ -C₈ -carbamyl, C₁-C₈ -alkoxycarbonyl, an unsubstituted or substituted heterocyclicradical which may or may not be quaternized, or unsubstituted orsubstituted C₁ -C₄ -alkyl,

R³ is unsubstituted or substituted alkyl, and

M is an oxygen bridge or an imino group having the structure ##STR7##and X and R² may form a ring interrupted by heteroatoms.

Radicals R³ may be the same or different and are, for example, methyl,ethyl, propyl, butyl, benzyl, tolyl, p-chlorobenzyl, cyanoethyl,hydroxyethyl, C₁ -C₄ -alkoxyethyl, 2-hydroxypropyl or carbamylmethyl.

Examples of radicals X are methyl, ethyl, propyl, butyl, cyano,methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl,butylaminocarbonyl, carbamyl, methoxycarbonyl, ethoxycarbonyl,benzimidazol-2-yl, N-methyl-benzimidazol-2-yl,N,N'-dimethyl-benzimidazol-2-ium, benzthiazol-2-yl,N-methyl-benzthiazol-2-ium, benzoxazol-2-yl andN-methyl-benzoxazol-2-ium.

Examples of preferred radicals R³ are methyl, ethyl, cyanoethyl andhydroxyethyl, and examples of preferred radicals X are cyano, methyl,carbamyl and C₁ -C₄ -alkylcarbamyl.

Anions A.sup.⊖ are organic or inorganic, and specific examples arefluoride, chloride, bromide, iodide, perchlorate, hydrogen sulfate,sulfate, aminesulfate, nitrate, dihydrogen phosphate, hydrogenphosphate, phosphate, bicarbonate, carbonate, methosulfate, ethosulfate,cyanate, thiocyanate, tetrachlorozincate, borate, tetrafluoborate,acetate, chloroacetate, cyanoacetate, hydroxyacetate, aminoacetate,methylaminoacetate, dichloroacetate and trichloroacetate,2-chloropropionate, 2-hydroxypropionate, glycolate, thioglycolate,thioacetate, phenoxyacetate, trimethylacetate, valerate, palmitate,acrylate, oxalate, malonate, crotonate, succinate, citrate,methylene-bis-thioglycolate, ethylene-bis-iminoacetate,nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate,chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate,phthalate, terephthalate, indolylacetate, chlorobenzenesulfonate,benzenesulfonate, toluenesulfonate, biphenylsulfonate andchlorotoluenesulfonate.

A compound of the formula I may be prepared, for example, by condensinga compound of the formula II

    [H.sub.2 A--B.sup.1 --AH.sub.2 ].sup.m.spsp.⊕ mA.sup.⊖II

with a compound of the formula III ##STR8## where B¹, B², A.sup.⊖, R¹and R have the stated meanings and m is a number up to 10, preferably 1,2, 3 or 4.

An alternative synthesis is to react a compound of the formula IV##STR9## with a compound of the formula V

    Y--B.sup.1 --Y                                             V

where Y is a radical of an anionic leaving group.

A compound of the formula I can also be prepared by reacting a compoundof the formula VI ##STR10## with a compound of the formula V, A¹ being,for example, ##STR11##

A compound of the formula I can also be prepared by reacting a compoundof the formula VII ##STR12## with a compound of the formula II to give acompound of the formula VIIa ##STR13## and then reacting this with anamine of the formula H₂ B².

Advantageously, the components are heated, in the presence of absence ofa solvent, to an elevated temperature, for example from 30° to 200° C.,preferably from 60° to 150° C., and a condensing agent, such as an acidor base, is then added. Specific examples of condensing agents are NaOH,KOH, MgO, Ca(OH)₂, primary, secondary or tertiary amines, HCl, HCOOH,CH₃ COOH, toluenesulfonic acid, zinc chloride, or a mixture such asNaOOCH₃ /CH₃ COOH, or triethylamine/CH₃ COOH.

Advantageous solvents are organic water-miscible compounds, eg. ethanol,glycol, glycerol, methylglycol, thiodiglycol, dimethylformamide,dimethylsulfoxide, acetamide, glacial acetic acid, acetic anhydride,formic acid and mixtures of such solvents with water. To produce fluiddye formulations it is possible to use alcohols, or more especiallywater, inorganic and organic acids and mixtures of these with water.

Details of how to conduct the reaction may be found in the Examples,where parts and percentages are by weight, unless stated otherwise.

The compounds of the formula I are particularly suitable for the wet-endcoloring of sized and unsized papers, and have a high affinity for bothligneous (groundwood-containing) and lignin-free paper pulps. Themajority of the dyes are substantive, and the waste water from thecoloring process is almost or completely colorless. The hues achievablerange from yellow to blue.

Compounds of particular importance are those of the formula VIII##STR14## where A, B¹, n, p and A.sup.⊖ have the meanings given forformula I and

R⁴ is C₁ -C₄ -alkyl, β-cyanoethyl, cyanomethyl, β-chloroethyl,β-hydroxyethyl, 2-hydroxy-3-chloropropyl or β-C₁ -C₄ -alkoxyethyl.

The radicals B¹, A and R⁴ may be identical or different.

Examples of preferred radicals are:

B¹ : ethylene, propylene, butylene, o-, m- and p-xylylene, p-diphenyleneand but-2-enylene and A:

EXAMPLE 1

10 ml of pyrrolidine are added to 30 parts of the dialdehyde of theformula 1 ##STR16## and 52 parts of the compound of the formula 2##STR17## in 50 ml of glycol at 70° C. and the mixture is kept at thistemperature for 2 hours. On adding 25 ml of glacial acetic acid, a fluidformulation of an oligomeric or polymeric dye of the formula 3 ##STR18##having good solubility in water and a long shelf life, is obtained. Thedye colors ligneous bleached and unbleached paper in yellow hues. Thewaste water is slightly colored or colorless.

EXAMPLE 2

18 Parts of the compound of the formula 4 ##STR19## and 15 parts of thedialdehyde of the formula 1, dissolved in 50 ml of thiodiglycol, areheated, in the presence of 5 ml of pyrrolidine, for 2 hours at 80° C.The batch is then poured into 300 ml of water and is acidified with 2 Nhydrochloric acid, and an orange dye of the formula 5 is isolated byadding sodium chloride/zinc chloride solution and then filtering off;when used to color paper, the dye gives a colorless or slightly coloredwaste water. ##STR20##

A similar reaction of an aldehyde of the formula ##STR21## with acompound of the general formula

    H.sub.2 A.sup.⊕ --B.sup.1 --A.sup.⊕ H.sub.2 2A.sup.⊖

gives a compound of the general formula ##STR22## of which more specificexamples are given in Table 1 below, A.sup.⊖ being chloride:

                                      TABLE 1                                     __________________________________________________________________________     B.sup.1         AH.sub.2                                                                                       ##STR23##              Hue                  __________________________________________________________________________     ##STR24##                                                                                     ##STR25##                                                                                      ##STR26##             yellow                  "             "                                                                                               ##STR27##             "                       "             "                                                                                               ##STR28##             "                       "             "                                                                                               ##STR29##             "                       "             "                                                                                               ##STR30##             "                      ##STR31##      "                                                                                               ##STR32##             "                       C.sub.2 H.sub.4                                                                              ##STR33##                                                                                      ##STR34##             "                       C.sub.4 H.sub.8                                                                              ##STR35##                                                                                      ##STR36##             "                       CH.sub.2CHCHCH.sub.2                                                                         ##STR37##                                                                                      ##STR38##             "                      ##STR39##                                                                                     ##STR40##                                                                                      ##STR41##             orange                  "             "                                                                                               ##STR42##             "                      ##STR43##      "                                                                                               ##STR44##             "                       C.sub.2 H.sub.4                                                                             "                                                                                               ##STR45##             "                       CH.sub.2CHCHCH.sub.2                                                                        "                                                                                               ##STR46##             "                       CH.sub.2CHCHCH.sub.2                                                                         ##STR47##                                                                                      ##STR48##             yellow                  "             "                                                                                               ##STR49##             "                      ##STR50##      "                "                      "                      ##STR51##      "                "                      "                      ##STR52##      "                "                      "                       "             "                                                                                               ##STR53##             "                       C.sub.2 H.sub.4                                                                             "                                                                                               ##STR54##             "                       C.sub. 4 H.sub.8                                                                            "                "                      "                      ##STR55##      "                "                      "                      ##STR56##                                                                                     ##STR57##                                                                                      ##STR58##             red                     C.sub.4 H.sub.8                                                                             "                                                                                               ##STR59##             "                       "                                                                                            ##STR60##       "                      "                       "                                                                                            ##STR61##       "                      blue                   ##STR62##      "                                                                                               ##STR63##             "                       C.sub.3 H.sub.6                                                                             "                "                      "                       C.sub.4 H.sub.8                                                                             "                "                      "                       "             "                                                                                               ##STR64##             "                       C.sub.4 H.sub.8                                                                              ##STR65##                                                                                      ##STR66##             reddish violet          "                                                                                            ##STR67##       "                      "                     __________________________________________________________________________

Instead of the pure bis-aldehydes of the formula ##STR68## it is ofcourse possible to use mixtures of bis-aldehydes which differ in respectof the bridge members B² or in respect of R and/or R¹. Equally, insteadof using the pure compound

    H.sub.2 A.sup.⊕ --B.sup.1 --A.sup.⊕ H.sub.2 2 A.sup.⊖

mixtures of this type of compound, in which the radicals A and/or B¹differ, may be employed. In this way it is possible to vary thesolubility, the affinity for paper and, in particular, the hue. Table 2below shows by way of an illustration, which applies to all thepreceding and subsequent Examples, that by the stated variation in thereactants it is possible to achieve a continuous change in hue, as wouldfor example also be possible by mixing the two polymers based onindividual starting compounds H₂ A-B¹ -AH₂ and ##STR69## It appearsreasonable to assume that the products synthesized in this way have thestructure of random copolymers, though it cannot be ruled out thathomopolymers may also form under the reaction conditions.

Following the general instruction of Example 1, the 52 parts of compound2 are replaced by the amounts, shown in the Table below, of compound ofthe formula 2 and compound of the formula 4.

                  TABLE                                                           ______________________________________                                        Amounts of compounds of the formula                                           2            4           Hue                                                  ______________________________________                                        46.8         3.6         yellowish orange                                     41.6         7.2         yellowish orange                                     36.4         10.8        orange                                               31.2         14.4        orange                                               26.0         18.0        orange                                               20.8         21.6        orange                                               15.6         25.2        orange                                               10.4         28.8        orange                                               5.2          32.4        orange                                               ______________________________________                                    

With increasing proportion of compound of the formula 4, the hue shiftsfrom strongly yellowish orange to reddish-orange.

Depending on the synthesis, end groups of the dyes of the formulae 3 and5 and of all the other dyes claimed are the radicals ##STR70## thereactive centers of which may or may not have been reacted further.Possible reactants for the free aldehyde group of the end group##STR71## are in principle those systems which are capable of reactingwith an aldehyde group, in particular condensable methylene-activecomponents, eg. malodinitrile. Suitable reactants for the free radicals--B¹ --AH₂.sup.⊕ A.sup.⊖ are in particular aldehydes, eg. benzaldehyde.In this context, the possibility of shading by using methylene-activecompounds which on condensation with p-aminobenzaldehydes give coloredcompounds of a different hue from the dye which is to be shaded is ofparticular importance.

If, for example, when synthesizing the dye of Example 1, 3 g ofN-methyl-γ-picolinium methosulfate are added to the reaction mixturebefore or after adding glacial acetic acid the dye obtained shows ashift in hue toward orange compared to the dye of Example 1.

Carbonyl-containing compounds may be used similarly for shading,provided they give condensation products of a different color than thatof the dye to be shaded. For example, the addition of 3 g ofp-dimethylaminobenzaldehyde to the reaction mixture of Example 1 at 60°C., before addition of glacial acetic acid, produces a shift in huetoward red compared to the dye of Example 1.

The degree of polymerization of the compounds substantially depends onthe reaction conditions, especially the reaction time and the reactiontemperature. The substantivity of the dyes on paper decreases slightlywith decreasing reaction time and decreasing reaction temperature, buton the other hand the brilliance of the colorations increases. Thetemperature variations shown in Table 2 below are typical of all theExamples given, unless stated otherwise.

                  TABLE 2                                                         ______________________________________                                        Amounts of chemicals employed as in Example 1                                 Temperature (°C.)                                                                       Time (h)                                                     ______________________________________                                        40               10                                                           50               7                                                            50               3                                                            50               1                                                            60               10                                                           60               2                                                            60               1                                                            70               5                                                            70               2                                                            70               1                                                            70               1/2                                                          70               1/4                                                          80               1                                                            90               2                                                            100              1/2                                                          110              2                                                            110              1                                                            120              1                                                            130              1/2                                                          140              2                                                            140              1                                                            140              1/2                                                          140              1/4                                                          150              1/2                                                          160              1/2                                                          170              1/2                                                          ______________________________________                                    

It is found in this series of experiments that under otherwise identicalreaction conditions, an increase in reaction time or an increase ofreaction temperature, in particular at >110° C., results in asubstantial decrease in brilliance. Equally, it becomes progressivelymore difficult to obtain concentrated fluid formulations of sufficientviscosity. The solubility in water remains substantially unaffected bythese variations of reaction time and reaction temperature.

Further compounds of particular importance are those of the formula IX##STR72## where A, B¹, B³, R², R⁴, n, p and A.sup.⊖ have the statedmeanings and

B¹, R², A and R⁴ may be identical or different.

Examples of preferred radicals are:

R⁴, A and B¹ : the radicals mentioned in connection with formula VIII,

B³ : ethylene, propylene, butylene, ##STR73## hexamethylene, and

R₂ : hydrogen, methyl, ethyl and hydroxyethyl.

EXAMPLE 3

5 ml of pyrrolidine are added to 42 parts of a compound of the formula 6##STR74## and 18 parts of a compound of the formula 4 in 50 ml ofthiodiglycol at 80° C., and the mixture is kept at this temperature for2 hours. On adding 25 ml of glacial acetic acid and 5 ml of water, afluid formulation of an oligomeric or polymeric dye of the formula 7##STR75## is obtained.

The dye colors groundwood, and bleached and unbleached cellulose, inorange hues, with very little coloration of the waste water.

Similarly, reaction of a bis-aldehyde of the general type ##STR76## witha compound of the general structure

    H.sub.2 A.sup.⊕ --B.sup.1⊕ --AH.sub.2 2 A.sup.⊖

gives a dye of the general formula IX.

Table 3 gives further examples of dyes of the formula IX, where A.sup.⊖is chloride.

                                      TABLE 3                                     __________________________________________________________________________    B.sup.3         AH.sub.2        B.sup.1        R.sup.2                                                                          R.sup.4                                                                          Hue                      __________________________________________________________________________    C.sub.2 H.sub.4                                                                                ##STR77##      C.sub.2 H.sub.4                                                                              H  CH.sub.3                                                                         orange                     "             "               "              CH.sub.3                                                                         "  "                        "               "               "              "  C.sub.2 H.sub.5                                                                  "                        "               "               "              "  "  "                        C.sub.3 H.sub.6 "               "              "  "  "                        C.sub.4 H.sub.8 "               "              "  "  "                        C.sub.5 H.sub.10                                                                              "               "              "  "  "                        C.sub.6 H.sub.12                                                                              "               "              "  "  "                          C.sub.2 H.sub.4                                                                             "                                                                                              ##STR78##     "  "  "                          C.sub.3 H.sub.6                                                                             "               "              "  "  "                        C.sub.4 H.sub.8 "               "              "  "  "                        C.sub.5 H.sub.10                                                                              "               "              "  CH.sub.3                                                                         "                          C.sub.6 H.sub.12                                                                             ##STR79##      "              H  CH.sub.3                                                                         yellow                     "             "               "              CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  "                          "             "                                                                                              ##STR80##     "  "  "                          C.sub.2 H.sub.4                                                                             "                                                                                              ##STR81##     "  "  "                          "                                                                                            ##STR82##      C.sub.4 H.sub.8                                                                              "  "  "                          "             "               CH.sub.2CHCHCH.sub.2                                                                         "  "  "                        C.sub.4 H.sub.8 "               CH.sub.2CCCH.sub.2                                                                           "  "  "                        C.sub.2 H.sub.4 "               C.sub.5 H.sub.10                                                                             "  "  "                         ##STR83##      "               C.sub.2 H.sub.4                                                                              "  "  "                         ##STR84##      "               "              "  "  "                         ##STR85##                                                                                     ##STR86##      "              H  "  blue                       C.sub.2 H.sub.4HNC.sub.3 H.sub.6                                                             ##STR87##      "              "  CH.sub.3                                                                         "                         ##STR88##      "               "              "  C.sub.2 H.sub.5                                                                  "                         ##STR89##      "               "              "  "  "                          C.sub.2 H.sub.4OC.sub.2 H.sub.4                                                              ##STR90##                                                                                     ##STR91##     "  "  red                       ##STR92##      "               CH.sub.2CHCHCH.sub.2                                                                         "  "  "                        __________________________________________________________________________

Further compounds of particular importance are those of the structure X##STR93## where A, B¹, p, n and A.sup.⊖ have the stated meanings and theradicals A may be identical or different.

Examples of preferred radicals B¹ are ethylene, propylene, butylene, o-,m- and p-xylylene, ##STR94##

EXAMPLE 4

5 ml of pyrrolidine are added to 21 parts of diphenyldialdehyde and 52parts of a compound of the formula 9 in 50 ml of glycol at 80° C., andthe mixture is kept at the same temperature for 2 hours. It is thenpoured into 500 ml of water, saturated sodium chloride solution is addedand the product is filtered off and dried. A yellow dye of the formula##STR95## is obtained in good yield. The dye may be used for coloringpaper. The waste water is colorless or pale yellow.

Similarly, reaction of diphenylaldehyde with compounds of the generalformula

    H.sub.2 A.sup.⊕ --B.sup.1⊕ --AH.sub.2

gives dyes of the general formula X.

Table 4 gives examples of other dyes of the formula X.

                                      TABLE 4                                     __________________________________________________________________________    B.sup.1                       AH.sub.2      Hue                               __________________________________________________________________________    C.sub.2 H.sub.4                                                                                              ##STR96##    yellow                            C.sub.4 H.sub.8               "             "                                  ##STR97##                    "             "                                  ##STR98##                    "             "                                  ##STR99##                    "             "                                  ##STR100##                   "             "                                  ##STR101##                   "             "                                  ##STR102##                   "             "                                  ##STR103##                   "             "                                     "                                                                                                        ##STR104##   yellowish orange                      "                                                                                                        ##STR105##   red                                ##STR106##                   "             "                                   C.sub.4 H.sub.8             "             "                                 __________________________________________________________________________

Further compounds of particular importance are those of the formula XI##STR107## where A, B², B¹, n, p, R⁴ and A.sup.⊖ have the statedmeanings,

A and R⁴ may be identical or different and

B⁴ is a bridge member which conforms to the general definition of B¹ butdoes not carry a positive charge and is not interrupted by ahetero-atom.

Examples of preferred radicals are:

B¹ and B⁴ : ethylene, propylene, butylene, o-, m- and p-xylylene andbut-2-enylene,

R⁴ : ethyl and methyl, and

B² : --HN--C₃ H₆ --NH--, --HN--C₂ H₄ --NH-- and --HN--C₆ H₁₂ --NH--.

EXAMPLE 5

33 Parts of a dialdehyde of the formula 8 ##STR108## and 52 parts of acompound of the formula 9 ##STR109## in 50 ml of glycol are heated inthe presence of 5 ml of pyrrolidine for 2 hours at 90° C. On adding 50ml of glacial acetic acid, a fluid formulation of a red dye of theformula 10 ##STR110## is obtained. The dye is very readily soluble inwater and dyes groundwood and bleached and unbleached cellulose inorange hues. The waste water is colorless or slightly colored.

Using a similar method, reaction of a bisaldehyde of the general formula##STR111## with a compound of the general formula

    H.sub.2 A.sup.⊕ --B.sup.4 --B.sup.2 --B.sup.4⊕ --AH.sub.2 2Cl.sup.⊖

gives a dye of the general formula XI.

Table 5 shows further examples of dyes of the formula XI, where A.sup.⊖is chloride.

                                      TABLE 5                                     __________________________________________________________________________    B.sup.1   B.sup.4       B.sup.2           AH.sub.2      R.sup.4                                                                          Hue                __________________________________________________________________________    C.sub.2 H.sub.4                                                                         C.sub.2 H.sub.4                                                                             HNC.sub.2 H.sub.4NH                                                                              ##STR112##   CH.sub.3                                                                         red                    "     C.sub.4 H.sub.8                                                                             "                 "             C.sub.2 H.sub.5                                                                  "                   ##STR113##                                                                             "             "                 "             "  "                   ##STR114##                                                                             "             "                 "             "  "                    C.sub.4 H.sub.8                                                                       "             HNC.sub.3 H.sub.6NH                                                                             "             "  "                  C.sub.4 H.sub.8                                                                         CH.sub.2CHCHCH.sub.2                                                                        "                 "             "  "                    "       "             "                                                                                                ##STR115##   "  orange              ##STR116##                                                                             CH.sub.2CHCHCH.sub.2                                                                        HNC.sub.3 H.sub.6NH                                                                              ##STR117##   C.sub.2 H.sub.5                                                                  orange                 "     "             HNC.sub.6 H.sub.12NH                                                                             ##STR118##   "  yellow                 "                                                                                    ##STR119##   "                 "             "  "                      "     "             HNC.sub.2 H.sub.4NH                                                                              ##STR120##   CH.sub.3                                                                         blue                    "    "             "                 "             C.sub.2 H.sub.5                                                                  "                    "       CH.sub.2CHCHCH.sub.2                                                                        "                 "             "  "                    "                                                                                      ##STR121##                                                                                  ##STR122##       "             "  "                  __________________________________________________________________________

Further compounds of particular importance are those of the formula XII##STR123## where B³, B², R², R⁴, A, p, A.sup.⊖ and n have the statedmeanings and

the symbols R², R⁴, T and A may each be identical or different.

Examples of preferred radicals are:

R², R⁴ and A: the radicals stated to be preferred for formula IX,

B³ : the radicals B¹ stated to be preferred for formula VIII and

B² : the radicals stated to be preferred for formula XI.

EXAMPLE 6

42 Parts of a dialdehyde of the formula 6 and 52 parts of a compound ofthe formula 9 in 50 ml of methylglycol are heated in the presence of 10ml of pyrrolidine for 2 hours at 80° C. On adding 70 ml of glacialacetic acid a fluid formulation of a dye of the formula ##STR124## isobtained. The dye may be used for coloring paper. The waste water isonly slightly colored.

Using a similar method, reaction of a bis-aldehyde of the generalformula ##STR125## with a compound of the general formula

    H.sub.2 A.sup.⊕ --B.sup.3 --B.sup.2 --B.sup.3⊕ --AH.sub.2 2Cl.sup.⊖

gives a dye of the general formula XII.

Table 6 below gives further examples of dyes of the formula XII.

                                      TABLE 6                                     __________________________________________________________________________    B.sup.1                                                                             B.sup.3        B.sup.2    AH.sub.2       R.sup.2                                                                          R.sup.4                                                                          Hue                      __________________________________________________________________________    C.sub.2 H.sub.4                                                                     C.sub.2 H.sub.4                                                                              HNC.sub.2 H.sub.4NH                                                                       ##STR126##    CH.sub.3                                                                         CH.sub.3                                                                         red                          " "              "          "              "  C.sub.2 H.sub.5                                                                  "                          "                                                                                  ##STR127##    "          "              "  "  "                          C.sub.3 H.sub.6                                                                   "              "          "              "  "  "                        C.sub.6 H.sub.12                                                                    "              "          "              "  "  "                        C.sub.4 H.sub.8                                                                     C.sub.4 H.sub.8                                                                              HNC.sub.3 H.sub.6NH                                                                      "              "  "  orange                     "   "              C.sub.2 H.sub.4                                                                          "              "  "  "                          "                                                                                  ##STR128##    HNC.sub.3 H.sub.6NH                                                                      "              "  "  "                            " "              "                                                                                         ##STR129##    C.sub.2 H.sub.5                                                                  "  yellow                     C.sub.2 H.sub.4                                                                   "              "                                                                                         ##STR130##    "  "  "                            " "              "          "              "  CH.sub.3                                                                         "                          "   "              "          "              CH.sub.3                                                                         "  "                          "   "              "                                                                                         ##STR131##    "  "  "                          C.sub.3 H.sub.6                                                                   CH.sub.2CHCHCH.sub.2                                                                         "          "              C.sub.2 H.sub.5                                                                  "  "                        C.sub.2 H.sub.4                                                                      ##STR132##    HNC.sub.2 H.sub.4NH                                                                       ##STR133##    "  C.sub.2 H.sub.5                                                                  blue                          "                                                                              C.sub.3 H.sub.6                                                                              "          "              "  CH.sub.3                                                                         "                          "   C.sub.4 H.sub.8                                                                              HNC.sub.3 H.sub.6NH                                                                      "              "  "  "                        __________________________________________________________________________

Further compounds of particular importance are those of the formula XIII##STR134## where X, M, p, n and A.sup.⊕ have the stated meanings and theradicals M and X may be identical or different.

Radicals B² are those, within the scope of the general definition given,which are derived from a triamine or amine of higher functionality, andin which one or more amino groups may be quaternized. Radicals B⁶ areradicals within the scope of the general definition of B¹ which do notcarry a quaternary charge.

Examples of preferred radicals are:

B⁶ : ethylene, propylene, p-phenylene and butylene,

M: oxygen, ##STR135##

EXAMPLE 7

A mixture of 17 parts of cyanoacetic acid and 37 parts of aceticanhydride is heated for 1 hour at 70° C. and then cooled to 40° C., and18 parts of a compound of the formula ##STR136## are added. The mixtureis then stirred for a further hour at 40° C. Thereafter 76 parts of abis-aldehyde of the formula ##STR137## are added and the mixture isheated for 6 hours at 80° C. On adding 100 parts of glacial acetic acid,a fluid formulation of a yellow dye of the formula ##STR138## isobtained. The dye may be used for coloring paper.

Using a similar method, reacton of a compound of the general formula

    E--B.sup.6 --E

where E may be OH or ##STR139## and where R² has the stated meanings,with a mixed anhydride of the formula ##STR140## where Q is the radicalof an organic or inorganic acid, preferably of acetic acid orhydrochloric acid, followed by condensation with a dialdehyde of thegeneral formula ##STR141## gives a dye of the general formula XIII.

Table 7 which follows shows further dyes of the general formula XIIIwhere X is CN. These dyes are yellow.

                                      TABLE 7                                     __________________________________________________________________________    B.sup.6          B.sup.2                     M                                __________________________________________________________________________     ##STR142##                                                                                     ##STR143##                 O                                    "                                                                                           ##STR144##                  "                                 C.sub.2 H.sub.4                                                                               ##STR145##                  "                                 C.sub.3 H.sub.6                                                                               ##STR146##                  "                                   "               "                        NH                                   "               "                                                                                                       ##STR147##                       ##STR148##         "                                                                                                       ##STR149##                          "               "                        O                                 ##STR150##                                                                                     ##STR151##                  "                                   "               "                        NH                                ##STR152##                                                                                     ##STR153##                 O                                __________________________________________________________________________

Further compounds of particular importance are those of the formula XIV##STR154## where X, M, B², n, p and A.sup.⊖ have the stated meanings,

the radicals M and X may be identical or different and

B⁵ is a bridge member, within the scope of the definition of B¹, whichcarries one or more positive charges.

Examples of preferred radicals are: ##STR155##

EXAMPLE 8

A mixture of 17 parts of cyanoacetic acid and 37 parts of aceticanhydride is heated for 1 hour at 70° C. and cooled to 40° C., and 41parts of a compound of the formula ##STR156## are added. Stirring iscontinued for 1 hour at 40° C. 28 parts of diphenylpiperazinedialdehydeare then added to the reaction mixture, which is heated for 7 hours at80° C. On adding 50 parts of glacial acetic acid, a fluid formulation ofa yellow dye of the formula ##STR157## is obtained. The dye colorsgroundwood and bleached and unbleached cellulose in yellow hues. Thewaste water is colorless or slightly colored.

Using a similar method, reaction of a compound of the general formula

    E--B.sup.5 --E

where

E may be OH or NH₂ and

B⁵ is a bridge member, within the scope of the definition of B¹, whichcarries one or more positive charges,

with a mixed anhydride of the formula ##STR158## where Q is the radicalof an organic or inorganic acid, preferably of acetic acid orhydrochloric acid, followed by condensation with a dialdehyde of thegeneral formula ##STR159## gives a day of the general formula XIV.

Table 8 below shows further dyes of the general formula XIV, where X isCN. These dyes are yellow.

                                      TABLE 8                                     __________________________________________________________________________    B.sup.5                   B.sup.2              M                              __________________________________________________________________________     ##STR160##                                                                                              ##STR161##          O                               ##STR162##                                                                                              ##STR163##          "                               ##STR164##                                                                                              ##STR165##          "                               ##STR166##                 "                  "                               ##STR167##                 "                  "                               ##STR168##                                                                                              ##STR169##          "                               ##STR170##                                                                                              ##STR171##          "                               ##STR172##                                                                                              ##STR173##          "                               ##STR174##                                                                                              ##STR175##          "                               ##STR176##                                                                                              ##STR177##          "                               ##STR178##                                                                                              ##STR179##          "                                  "                                                                                                    ##STR180##                                                                                         ##STR181##                        "                                                                                                    ##STR182##          "                               ##STR183##                                                                                              ##STR184##          O                               ##STR185##                                                                                              ##STR186##          "                               ##STR187##                                                                                              ##STR188##          "                                  "                                                                                                    ##STR189##          "                                  "                                                                                                    ##STR190##          "                              __________________________________________________________________________

EXAMPLE 9

50 Parts of a compound of the formula ##STR191## and 33 parts of adialdehyde of the formula 8 in 50 ml of glycol are heated to 80° C., 2ml of pyrrolidine are added and the mixture is kept at 80° C. for 2hours. On adding 100 ml of glacial acetic acid, a fluid formulation of ayellow dye of the formula ##STR192## is obtained. The dye colors paperin yellow hues, with little color in the waste water.

Using a similar method, reaction of a compound of the general formula##STR193## where X is an electron-attracting substituent other than CN,with a dialdehyde of the general formula ##STR194## gives a dye of thegeneral formula XIV.

Table 9 which follows shows further dyes of the general formula XIV.These dyes are yellow, unless stated otherwise.

                                      TABLE 9                                     __________________________________________________________________________    B.sup.5                   B.sup.2            X            M                   __________________________________________________________________________     ##STR195##                                                                                              ##STR196##                                                                                       ##STR197##  O                        "                                                                                                   ##STR198##          "          "                        "                                                                                                   ##STR199##          "          "                        "                      "                                                                                               ##STR200##  "                   __________________________________________________________________________    B.sup.5         B.sup.2                     X         M    Hue                __________________________________________________________________________     ##STR201##                                                                                    ##STR202##                                                                                                ##STR203##                                                                             O                        ##STR204##                                                                                    ##STR205##                   "       "                           "              "                          "       NH                          "                                                                                          ##STR206##                   "       O                        ##STR207##        "                                                                                                       ##STR208##                                                                             "    orange                 "                                                                                          ##STR209##                                                                                                ##STR210##                                                                             "    yellow                 "                                                                                          ##STR211##                                                                                                ##STR212##                                                                             "    "                      "              "                                                                                                       ##STR213##                                                                             "    "                      "              "                          "       NH   "                  __________________________________________________________________________

We claim:
 1. A paper stock dyed with a polymeric dye of the formula I##STR214## wherein, B¹ is a bridge member selected from the groupconsisting of: lower alkylene, substituted lower alkylene, loweralkylene and substituted lower alkylene containing --NH--, --S--, --O--,carbamyl, carbonyloxy, ##STR215## phenylene, substituted phenylene,napthylene, cycloalkylene, and heteroatom containing cycloalkyleneradicals;B² is a direct bond between dye molecule units or is a bridgemember selected from the group consisting of: ##STR216## wherein R islower alkylene, hydroxy-substituted lower alkylene, C₁ -C₄ alkoxy,chloro, bromo or phenylene radicals; R² is hydrogen, lower alkyl, orsubstituted lower alkyl radical; B¹ is as already defined; and r is aninteger from 1 to 6, n is a number>1, p is the number of positivecharges, A⁻ is an anion, R is hydrogen, chloro, bromo, hydroxyl, C₁ -C₈alkyl, nitro, C₁ -C₈ alkoxy, C₁ -C₈ alkoxycarbonyl, cyano,hydroxycarbonyl, unsubstituted or substituted carbamyl or unsubstitutedor substituted amino, R¹ is hydrogen, chloro, hydroxyl, C₁ -C₄ alkyl orC₁ -C₄ alkoxy or, R and R¹ together are an unsubstituted or substitutedfused ring, or R and R¹ together with B² are a heterocyclic radical, Tis a straight-chain or branched alkylene radical which is unsubstitutedor substituted by hydroxyl, C₁ -C₄ alkoxy, chlorine or bromine, or is aphenylene radical, A is the radical of a methylene-active compoundselected from the group consisting of: ##STR217## wherein R and R² areas already defined; R³ is lower alkyl or substituted lower alkyl; X ishydrogen, cyano, C₁ -C₈ carbamyl, C₁ -C₄ alkyl, or a heterocyclicradical; M is an oxygen atom or an imino group, having the structure##STR218## and X and M may form a ring structure incorporatingheteroatoms therein.
 2. The paper stock dyed with a polymeric dye as inclaim 1, wherein the dye has the formula: ##STR219## wherein, A, B¹, n,p and A⁻ are as claimed in claim 1; and R⁴ is C₁ -C₄ alkyl,β-cyanoethyl, cyanomethyl, β-chloroethyl, β-hydroxyethyl,2-hydroxy-3-chloropropyl, and B-C₁ -C₄ -alkoxyethyl.